Electrocatalysis for CO₂conversion: from fundamentals to value-added products

Chemical Society Reviews, Год журнала: 2021, Номер 50(8), С. 4993 - 5061

Опубликована: Янв. 1, 2021

This timely and comprehensive review mainly summarizes advances in heterogeneous electroreduction of CO₂: from fundamentals to value-added products.

Язык: Английский

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Scalable Production of Efficient Single-Atom Copper Decorated Carbon Membranes for CO₂ Electroreduction to Methanol

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(32), С. 12717 - 12723

Опубликована: Июль 26, 2019

Electrocatalytic reduction reaction of CO2 (CO2RR) is an effective way to mitigate energy and environmental issues. However, very limited catalysts are capable converting resources into high-value products such as hydrocarbons or alcohols. Herein, we first propose a facile strategy for the large-scale synthesis isolated Cu decorated through-hole carbon nanofibers (CuSAs/TCNFs). This CuSAs/TCNFs membrane has excellent mechanical properties can be directly used cathode CO2RR, which could generate nearly pure methanol with 44% Faradaic efficiency in liquid phase. The self-supporting structure greatly reduces embedded metal atoms produces abundant efficient single atoms, actually participate eventually causing -93 mA cm-2 partial current density C1 more than 50 h stability aqueous solution. According DFT calculations, possess relatively higher binding *CO intermediate. Therefore, further reduced like methanol, instead being easily released from catalyst surface CO product. report may benefit design high-yield single-atom other electrocatalytic reactions.

Язык: Английский

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Strategies in catalysts and electrolyzer design for electrochemical CO₂reduction toward C₂₊products

Science Advances, Год журнала: 2020, Номер 6(8)

Опубликована: Фев. 21, 2020

Recent progress about electrochemical CO 2 reduction toward C 2+ products is reviewed.

Язык: Английский

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Protecting Copper Oxidation State via Intermediate Confinement for Selective CO₂ Electroreduction to C₂₊ Fuels

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(13), С. 6400 - 6408

Опубликована: Март 16, 2020

Selective and efficient catalytic conversion of carbon dioxide (CO2) into value-added fuels feedstocks provides an ideal avenue to high-density renewable energy storage. An impediment enabling deep CO2 reduction oxygenates hydrocarbons (e.g., C2+ compounds) is the difficulty coupling carbon-carbon bonds efficiently. Copper in +1 oxidation state has been thought be active for catalyzing formation, whereas it prone being reduced Cu0 at cathodic potentials. Here we report that catalysts with nanocavities can confine intermediates formed situ, which turn covers local catalyst surface thereby stabilizes Cu+ species. Experimental measurements on multihollow cuprous oxide exhibit a Faradaic efficiency 75.2 ± 2.7% partial current density 267 13 mA cm-2 large C2+-to-C1 ratio ∼7.2. Operando Raman spectra, conjunction X-ray absorption studies, confirm species as-designed are well retained during reduction, leads marked selectivity rate.

Язык: Английский

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Photoinduction of Cu Single Atoms Decorated on UiO-66-NH₂ for Enhanced Photocatalytic Reduction of CO₂ to Liquid Fuels

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(45), С. 19339 - 19345

Опубликована: Окт. 29, 2020

Photocatalytic reduction of CO2 to value-added fuels is a promising route reduce global warming and enhance energy supply. However, poor selectivity low efficiency catalysts are usually the limiting factor their applicability. Herein, photoinduction method was developed achieve formation Cu single atoms on UiO-66-NH2 support (Cu SAs/UiO-66-NH2) that could significantly boost photoreduction liquid fuels. Notably, SAs/UiO-66-NH2 achieved solar-driven conversion methanol ethanol with an evolution rate 5.33 4.22 μmol h-1 g-1, respectively. These yields were much higher than those pristine nanoparticles/UiO-66-NH2 composites. Theoretical calculations revealed introduction SAs greatly facilitates CHO* CO* intermediates, leading excellent toward ethanol. This study provides new insights for designing high-performance catalyst photocatalytic at atomic scale.

Язык: Английский

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Electrocatalytic Refinery for Sustainable Production of Fuels and Chemicals

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(36), С. 19572 - 19590

Опубликована: Фев. 19, 2021

Abstract Compared to modern fossil‐fuel‐based refineries, the emerging electrocatalytic refinery (e‐refinery) is a more sustainable and environmentally benign strategy convert renewable feedstocks energy sources into transportable fuels value‐added chemicals. A crucial step in conducting e‐refinery processes development of appropriate reactions optimal electrocatalysts for efficient cleavage formation chemical bonds. However, compared well‐studied primary (e.g., O 2 reduction, water splitting), mechanistic aspects materials design complex are yet be settled. To address this challenge, herein, we first present fundamentals heterogeneous electrocatalysis some reactions, then implement these establish framework by coupling situ generated intermediates (integrated reactions) or products (tandem reactions). We also set principles strategies efficiently manipulate reaction pathways.

Язык: Английский

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Regulating the Coordination Environment of MOF‐Templated Single‐Atom Nickel Electrocatalysts for Boosting CO₂ Reduction

Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(7), С. 2705 - 2709

Опубликована: Дек. 10, 2019

The general synthesis and control of the coordination environment single-atom catalysts (SACs) remains a great challenge. Herein, host-guest cooperative protection strategy has been developed to construct SACs by introducing polypyrrole (PPy) into bimetallic metal-organic framework. As an example, introduction Mg2+ in MgNi-MOF-74 extends distance between adjacent Ni atoms; PPy guests serve as N source stabilize isolated atoms during pyrolysis. result, series (named NiSA -Nx -C) with different numbers have fabricated controlling pyrolysis temperature. Significantly, -N2 -C catalyst, lowest number, achieves high CO Faradaic efficiency (98 %) turnover frequency (1622 h-1 ), far superior those -N3 -N4 -C, electrocatalytic CO2 reduction. Theoretical calculations reveal that low number sites is favorable formation COOH* intermediate thus accounts for its activity.

Язык: Английский

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Heterogeneous Single‐Atom Catalysts for Electrochemical CO₂ Reduction Reaction

Advanced Materials, Год журнала: 2020, Номер 32(34)

Опубликована: Июль 9, 2020

The electrochemical CO2 reduction reaction (CO2 RR) is of great importance to tackle the rising concentration in atmosphere. RR can be driven by renewable energy sources, producing precious chemicals and fuels, with implementation this process largely relying on development low-cost efficient electrocatalysts. Recently, a range heterogeneous potentially single-atom catalysts (SACs) containing non-precious metals coordinated earth-abundant elements have emerged as promising candidates for RR. Unfortunately, real catalytically active centers key factors that govern catalytic performance these SACs remain ambiguous. Here, ambiguity addressed developing fundamental understanding RR-to-CO SACs, CO accounts major product from SACs. mechanism, rate-determining steps, control activity selectivity are analyzed both experimental theoretical studies. Then, synthesis, characterization, discussed. Finally, challenges future pathways highlighted hope guiding design promote understand

Язык: Английский

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Active Site Engineering in Porous Electrocatalysts

Advanced Materials, Год журнала: 2020, Номер 32(44)

Опубликована: Июль 14, 2020

Abstract Electrocatalysis is at the center of many sustainable energy conversion technologies that are being developed to reduce dependence on fossil fuels. The past decade has witnessed significant progresses in exploitation advanced electrocatalysts for diverse electrochemical reactions involved electrolyzers and fuel cells, such as hydrogen evolution reaction (HER), oxygen reduction (ORR), CO 2 (CO RR), nitrogen (NRR), (OER). Herein, recent research advances made porous these five important reviewed. In discussions, an attempt highlight advantages multiobjective optimization surface active sites including not only their density accessibility but also intrinsic activity. First, current knowledge about electrocatalytic briefly summarized. Then, mechanisms above‐mentioned (HER, ORR, RR, NRR, OER), challenges faced by reactions, efforts meet using examined. Finally, future directions synthetic strategies leading materials, insights into sites, standardized tests performance requirements discussed.

Язык: Английский

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Controlling the Oxidation State of the Cu Electrode and Reaction Intermediates for Electrochemical CO₂ Reduction to Ethylene

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(6), С. 2857 - 2867

Опубликована: Янв. 20, 2020

Understanding the role of oxidation state Cu surface and surface-adsorbed intermediate species in electrochemical CO2 reduction is crucial for development selective CO2-to-fuel electrocatalysts. In this study, mechanism over catalysts with various states was studied by using situ surface-enhanced infrared absorption spectroscopy (SEIRAS), soft X-ray (Cu L-edge), online gas chromatography measurements. The atop-adsorbed CO (COatop) obtained on electrodeposited which primarily has Cu(I). COatop further reduced, followed formation C1 product such as CH4. residual bridge-adsorbed (CObridge) formed as-prepared Cu(0) inhibits hydrocarbon formation. contrast, CV-treated electrode prepared oxidizing contains different amounts Cu(I) states. major theme work that SEIRAS results show coexistence CObridge reaction intermediates during selectivity CO2-to-ethylene conversion enhanced electrode. modulated method exhibit well electrocatalytic properties.

Язык: Английский

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